HRP920669A2 - Aqueous, stable suspensions of water insoluble silicates which are able to bind calcium ions and their use in the production of washing and cleaning agents - Google Patents
Aqueous, stable suspensions of water insoluble silicates which are able to bind calcium ions and their use in the production of washing and cleaning agents Download PDFInfo
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- HRP920669A2 HRP920669A2 HRP-284/92A HRP920669A HRP920669A2 HR P920669 A2 HRP920669 A2 HR P920669A2 HR P920669 A HRP920669 A HR P920669A HR P920669 A2 HRP920669 A2 HR P920669A2
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- washing
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- 239000000725 suspension Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 21
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title description 23
- 238000005406 washing Methods 0.000 title description 19
- 239000012459 cleaning agent Substances 0.000 title description 15
- 150000004760 silicates Chemical class 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 4
- 101150020052 AADAT gene Proteins 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000004435 Oxo alcohol Substances 0.000 abstract description 4
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract 2
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 abstract 1
- -1 aluminum silicates Chemical class 0.000 description 31
- 239000004615 ingredient Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 2
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- RUYJNKYXOHIGPH-UHFFFAOYSA-N dialuminum;trioxido(trioxidosilyloxy)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] RUYJNKYXOHIGPH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
Poznato je da se za pranje i čišćenje čvrstih materijala, posebno tekstila, koriste sredstva za pranje i čišćenje, kod kojih ulogu vezanja kalcijevog kompleksa preuzimaju od fosfita, potpuno ili djelomično, aluminijevi silikati vrlo fino dispergirani u vodi, netopivi u vodi, sposobni za vezanje kalcija, a koji u općem slučaju sadrže vezanu vodu (vidi DE-OS 24 12 837). It is known that for the washing and cleaning of solid materials, especially textiles, washing and cleaning agents are used, in which the role of binding the calcium complex is taken over by phosphites, completely or partially, aluminum silicates very finely dispersed in water, insoluble in water, capable of binding of calcium, which generally contain bound water (see DE-OS 24 12 837).
Pri tome radi se o spojevima opće formule I: These are compounds of the general formula I:
(Kat2/nO)x⋅Me2O3⋅(SiO2)y (I), (Kat2/nO)x⋅Me2O3⋅(SiO2)y (I),
u kojoj Kat označava kation zamjenljiv kalcijem vrijednosti n, x je broj od 0,7 do 1,5 Me aluminija, a y je broj od 0,8 do 6, ponajprije od 1,3 do 4. in which Kat denotes a calcium exchangeable cation of value n, x is a number from 0.7 to 1.5 Me aluminum, and y is a number from 0.8 to 6, preferably from 1.3 to 4.
Kao kation u obzir dolazi prije svega natrij, ali se može zamijeniti litijem, kalijem, amonijem ili magnezijem. The most common cation is sodium, but it can be replaced by lithium, potassium, ammonium or magnesium.
Gore definirani spojevi, sposobni za vezanje kalcija, radi pojednostavljenja u daljnjem tekstu zvat će se "aluminijski silikati". Ovo posebno vrijedi za ponajprije primjenljive natrij-aluminijeve silikate: svi podaci dati za njihovu primjenu prema izumu i svi podaci o njihovoj proizvodnji i svojstvima vrijede za sve gore definirane spojeve. The compounds defined above, capable of binding calcium, will be called "aluminum silicates" in the following text for the sake of simplification. This is especially true for primarily applicable sodium aluminum silicates: all data given for their application according to the invention and all data on their production and properties apply to all compounds defined above.
Alumijski silikati posebno su pogodni za primjenu kod sredstava za pranje i čišćenje, imaju sposobnost vezanja kalcija od 50 do 200 mg CaO/g bezvodnog aluminijskog silikata. Aluminum silicates are particularly suitable for use in washing and cleaning agents, they have the ability to bind calcium from 50 to 200 mg CaO/g of anhydrous aluminum silicate.
Kad se u budućem bude spominjao bezvodni aluminijski silikat, time će se smatrati stanje aluminijskih silikata koje se postiže sušenjem pri 800°C tijekom 1 sata. Pri takovom sušenju potpuno se uklanjaju i slobodna i vezana voda. When anhydrous aluminum silicate is mentioned in the future, it will be considered the condition of aluminum silicates that is achieved by drying at 800°C for 1 hour. During such drying, both free and bound water are completely removed.
Kod proizvodnje sredstava za pranje i čišćenje, u kojima, pored uobičajenih sastojaka takovih sredstava, ima i aluminijskih silikata, kako je gore definirano, ponajprije se polazi od vlažnih aluminijskih silikata, npr. kakvi su još prije spomenute proizvodnje. Pri tome se vlažni sastojci miješaju najmanje s jednim dijelom ostalih sastojaka materijala koji će se proizvoditi i smjesa se podvrgava poznatim postupcima, kao npr. sušenju raspršivanjem, da se dobije krajnji proizvod u obliku sredstva za pranje ili čišćenje, npr. u obliku pogodnom za sipanje. U okviru ranije opisanog postupka proizvodnje sredstava za pranje i čišćenje aluminijski silikati nabavljaju se, odnosno upotrebljavaju u obliku vodene suspenzije. Pri tome su bila poželjna stanovita poboljšanja svojstava suspenzija aluminijskih silikata dispergiranih u vodenoj fazi - npr. postojanosti suspenzije i prikladnost za pumpanje. In the production of washing and cleaning agents, in which, in addition to the usual ingredients of such agents, there are also aluminum silicates, as defined above, the starting point is primarily wet aluminum silicates, for example, such as those of the previously mentioned production. In doing so, the wet ingredients are mixed with at least a part of the other ingredients of the material to be produced and the mixture is subjected to known processes, such as spray drying, to obtain the final product in the form of a washing or cleaning agent, e.g. in a form suitable for pouring. . As part of the previously described production process for washing and cleaning agents, aluminum silicates are obtained or used in the form of an aqueous suspension. In doing so, certain improvements in the properties of suspensions of aluminum silicates dispersed in the aqueous phase were desired - for example, stability of the suspension and suitability for pumping.
Poznato je da se za stvaranje suspenzija aluminijskih silikata koriste alkilfenoletilen-adukti (DE-A 26 15 698). Na osnovu narasle ekološke svijesti posebna pažnja posvećuje se sposobnostima biološkog raspadanja. It is known that alkylphenolethylene adducts (DE-A 26 15 698) are used to create suspensions of aluminum silicates. On the basis of increased environmental awareness, special attention is paid to the ability of biological decomposition.
Iz DE-A 32 09 631 poznata je upotreba nonilfenol-etoksilata. Temeljem svog benzolovog prstena ovi spojevi vrijede kao teško razgradljivi, pri čemu posebno postoji opasnost stvaranja otrovnog nonilfenola kao metastabilnog proizvoda razgradnje. Stoga je njemačka industrija odustala od upotrebe nonilfenoloksilata u proizvodnji sredstava za pranje i čišćenje. The use of nonylphenol ethoxylate is known from DE-A 32 09 631. On the basis of their benzene ring, these compounds are considered difficult to degrade, where there is a particular danger of the formation of toxic nonylphenol as a metastable degradation product. Therefore, the German industry abandoned the use of nonylphenoloxylate in the production of washing and cleaning agents.
Iz DE-A 34 44 311 poznata je upotreba izo-tridecilalkohol-oksilata. Pri tome, radi se o razgranatim lančastim alkoholima, postotka razgranatosti od najmanje 50%; nepregledne smjese izomera, često sa svim mogućim ograncima kao metil, etil, propil, izo-propil, i dr. The use of iso-tridecyl alcohol oxylate is known from DE-A 34 44 311. At the same time, we are dealing with branched chain alcohols, with a branching percentage of at least 50%; countless mixtures of isomers, often with all possible branches such as methyl, ethyl, propyl, iso-propyl, etc.
Iz DE-A 37 19 042 poznata je upotreba smjese dvaju oksoalkohol-etoksilata gormule R-(OCH2)n-OH. Kod visokih koncentracija ovdje se nažalost pri sobnim temperaturama postiže previsoka viskoznost. From DE-A 37 19 042 the use of a mixture of two oxoalcohol-ethoxylates of the gormula R-(OCH2)n-OH is known. At high concentrations, unfortunately too high a viscosity is achieved here at room temperatures.
Predmet izuma je vodena, postojana suspenzija silikata netopivog u vodi, sposobnog za vezanje kalcijevih iona, koja se može pumpati, a koja je obilježena time, da svedeno na ukupnu masu vodene suspenzije The subject of the invention is an aqueous, stable suspension of silicate insoluble in water, capable of binding calcium ions, which can be pumped, and which is characterized by the fact that it is reduced to the total mass of the aqueous suspension
A) kao silikat sposoban za vezanje kalcija sadrži 0,5 do 80% mas. fino dispergiranog, sintetički proizvedenog spoja s vezanom s vodom, prema općoj formuli I A) as a silicate capable of binding calcium contains 0.5 to 80% by weight. finely dispersed, synthetically produced water-bound compound, according to the general formula I
(Kat2/nO)x·Me2O3·(SiO2)y (I), (Kat2/nO)x·Me2O3·(SiO2)y (I),
u kojoj Kat označava kation vrijednosti n, zamljenljiv s kalcijem, x je broj od 0,7 do 1,5, Me bor ili aluminij, a y je broj od 0,5 do 6, i in which Kat denotes a cation of value n, exchangeable with calcium, x is a number from 0.7 to 1.5, Me is boron or aluminum, and y is a number from 0.5 to 6, and
B) kao sastojak disperznog djelovanja upotrebljava se smjesa od najmanje dva oksoalkohol-etoksilata formule II B) a mixture of at least two oxoalcohol-ethoxylates of formula II is used as a dispersing ingredient
R-(OCH2CH2)n-OH (II), R-(OCH2CH2)n-OH (II),
pri čemu R = C10-C15 alkil stupnja razgranatosti od 0 do 90% linearno i 100 do 10% jednostruko razgranatog s metilom, gdje where R = C10-C15 alkyl with a degree of branching from 0 to 90% linear and 100 to 10% monobranched with methyl, where
n = 3 - 5,25 mola EO kod komponente 1, n = 3 - 5.25 mol EO in component 1,
n = 5,5 - 7,0 mola EO kod komponente 2, i n = 5.5 - 7.0 moles of EO at component 2, i
C) jedan polietilenglikol srednje molekulske mase od 200 do 2000, pri čemu maseni udio komponenata B i C, svedeno na suspenziju, je od 0,5 do 6, ponajprije od 1 do 2 mas. %, a posebno od 1,4 do 1,6 mas. %. C) one polyethylene glycol with an average molecular weight of 200 to 2000, whereby the mass fraction of components B and C, reduced to a suspension, is from 0.5 to 6, preferably from 1 to 2 wt. %, and especially from 1.4 to 1.6 wt. %.
U suspenziji prema izumu komponenta A može biti u kristaliničnom obliku. In the suspension according to the invention, component A can be in crystalline form.
U formuli I broj y komponente A može biti od 1,3 do 4. In formula I, the number y of component A can be from 1.3 to 4.
Kristalinična komponenta A u izvedbi s prednošću može biti zeolit tipa A. The crystalline component A can preferably be a type A zeolite.
Prethodno navedeni spojevi bitni su sastojci suspenzije prema izumu. Suspenzija prema izumu može sadržavati nadalje i druge sastojke, kao npr. dodatke za suzbijanje stvaranja pjene, odnosno sredstva za poboljšanje otapanja, koja poboljšavaju topivost dodanih sredstava za dispergiranje u vodenoj fazi. Dodaci za suzbijanje pjene mogu biti uobičajena sredstva za suzbijanje pjene, npr. sapun za suzbijanje pjene, silikonsko sredstvo za suzbijanje pjene, derivati triazina koji suzbijaju stvaranje pjene, i koji su svi poznati stručnjacima i uvedeni. Ovakav dodatak u općem slučaju nije neophodan; međutim, kod sredstava za dispergiranje koja uzrokuju stvaranje pjene - posebno kod viših alkilbenzolskih sulfonskih kiselina - on može biti poželjan. The aforementioned compounds are essential ingredients of the suspension according to the invention. The suspension according to the invention may also contain other ingredients, such as additives to suppress the formation of foam, i.e. agents to improve dissolution, which improve the solubility of the added dispersing agents in the aqueous phase. The antifoam additives may be conventional antifoam agents, eg, antifoam soap, silicone antifoam, antifoam triazine derivatives, all of which are known and practiced in the art. Such an addition is generally not necessary; however, with foaming dispersants - especially higher alkylbenzene sulfonic acids - it may be desirable.
Također niti dodatak tvari za poboljšanje otapanja u općem slučaju nije potreban, međutim, može biti indiciran kad suspenzija prema izumu kao stabilizator sadrži jedan hidrofilni, ali u vodi slabo topiv koloid, kao npr. polivinilalkohol. Od prednosti je koristiti npr. jedno sredstvo za otapanje - kao što je natrij-toluolsulfonat. Also, the addition of substances to improve dissolution is generally not necessary, however, it may be indicated when the suspension according to the invention contains a hydrophilic, but poorly water-soluble colloid, such as polyvinyl alcohol, as a stabilizer. It is advantageous to use, for example, one solvent - such as sodium toluenesulfonate.
Udio sredstva za poboljšanje otapanja u ukupnoj suspenziji može biti npr. istog reda veličine kao i udio stabilizatora. Daljnji spojevi, pogodni kao sredstva za poboljšanje otapanja, poznati su stručnjacima; pogodna su hidrofobna sredstva kao npr. benzosulfonska kiselina, ksilolsulfonska kiselina, odnosno njihove soli ili također oktilsulfat. The proportion of the dissolution enhancer in the total suspension can be, for example, of the same order of magnitude as the proportion of the stabilizer. Further compounds suitable as dissolution enhancers are known to those skilled in the art; hydrophobic agents such as benzosulfonic acid, xylenesulfonic acid, or their salts or also octylsulfate are suitable.
Kod svih navoda o "koncetraciji aluminijskih silikata", o "sadržaju čvrste tvari" ili o sadržaju "aktivne tvari" (= AS) misli se na stanje aluminijskih silikata, koje se postiže nakon jednosatnog sušenja pri 800°C. Pri takvom sušenju praktički se potpuno uklanja sva adhezijska i vezana voda. All statements about "concentration of aluminum silicates", about "content of solid matter" or about the content of "active substance" (= AS) refer to the state of aluminum silicates, which is achieved after drying for one hour at 800°C. During such drying, practically all adhesive and bound water is completely removed.
Kod komponente A može se raditi o amorfnim ili kristaliničnim proizvodima, pri čemu se mogu, sasvim razumljivo, koristiti i mješavine amorfnih i kristaliničnih, a također i djelomično kristaliničnih proizvoda. Aluminijevi silikati mogu, naravno, biti iz prirodnih izvora ili proizvedeni sintetički, pri čemu sintetički proizvedeni imaju prednost. Proizvodnja se može provesti npr. reakcijom silikata topivih u vodi s aluminatima topivim u vodi, u prisutnosti vode. U tom cilju mogu se međusobno miješati vodene otopine polaznih tvari, ili se jedna komponenta, u čvrstom stanju, može se miješati s drugom, koja se nalazi u vodenoj otopini. Component A can be amorphous or crystalline products, and mixtures of amorphous and crystalline, as well as partially crystalline products can, of course, be used. Aluminum silicates can, of course, be from natural sources or produced synthetically, with synthetically produced having an advantage. Production can be carried out, for example, by reacting water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of starting materials can be mixed with each other, or one component, in a solid state, can be mixed with another, which is in an aqueous solution.
Također, miješanjem obaju komponenata u čvrstom stanju, u prisutnosti vode, dobivaju se željeni aluminijski silikati. Također, aluminijski silikati mogu se proizvesti iz Al(OH)3, Al2O3 ili SiO2 reakcijom s alkalnim silikatom ili otopinom aluminata. Proizvodnja se može obavljati i prema drugim poznatim postupcima. Izum se posebno odnosi na aluminijske silikate, koji imaju trodimenzionalnu strukturu prostorne rešetke. Also, by mixing both components in a solid state, in the presence of water, the desired aluminum silicates are obtained. Also, aluminum silicates can be produced from Al(OH)3, Al2O3 or SiO2 by reaction with alkali silicate or aluminate solution. Production can also be carried out according to other known procedures. The invention particularly relates to aluminum silicates, which have a three-dimensional spatial lattice structure.
Željena svojstva vezanja kalcija, koja leže u rasponu od 100 do 200 mg CaO/g, a najčešće između otprilike 100 do 180 mg CaO/g AS, dobivaju se prije svega kod spojeva sastava: The desired calcium binding properties, which lie in the range of 100 to 200 mg CaO/g, and most often between approximately 100 to 180 mg CaO/g AS, are obtained primarily with compounds of the composition:
0,7 - 1,1 Na2O⋅Al2O3⋅1, 3 - 3,3 SiO2 0.7 - 1.1 Na2O⋅Al2O3⋅1, 3 - 3.3 SiO2
Ova zbirna formula obuhvaća dva tipa različitih kristalnih struktura (odnosno njihovih nekristaliziranih predproizvoda), koji se razlikuju i svojim zbirnim formulama. To su: This summary formula includes two types of different crystal structures (that is, their non-crystallized precursors), which also differ in their summary formulas. These are:
a) 0,7 - 1,1 Na2O⋅Al2O3⋅1,3-2,4 SiO2 a) 0.7 - 1.1 Na2O⋅Al2O3⋅1.3-2.4 SiO2
b) 0,7 - 1,1 Na2O⋅Al2O3⋅2,4 -3,3 SiO2 b) 0.7 - 1.1 Na2O⋅Al2O3⋅2.4 -3.3 SiO2
Razlike kristalne strukture vide se na rentgenskim difrakcijskim snimkama. Differences in the crystal structure can be seen on X-ray diffraction images.
Vodena suspenzija postojećeg amorfnog ili kristaliničnog aluminijskog silikata može se odvojiti filtracijom od zaostale vodene otopine i osušiti pri temperaturi od npr. 50 do 400°C. Ovisno o uvjetima sušenja proizvod sadrži manje ili više vezane vode. Tako visoke temperature sušenja uglavnom se ne preporučuju; kad je aluminijski silikat predviđen za upotrebu u sredstvima za pranje i čišćenje svrhovito je ne ići iznad 200°C. The aqueous suspension of the existing amorphous or crystalline aluminum silicate can be separated by filtration from the remaining aqueous solution and dried at a temperature of, for example, 50 to 400°C. Depending on the drying conditions, the product contains more or less bound water. Such high drying temperatures are generally not recommended; when aluminum silicate is intended for use in washing and cleaning agents, it is advisable not to go above 200°C.
Međutim, aluminijski silikati nakon proizvodnje uopće se ne moraju sušiti radi proizvodnje prema izumu; čak štoviše - a to je od posebne prednosti - može se koristiti aluminijski silikat još vlažan od proizvodnje. Za proizvodnju suspenzije mogu se koristiti i aluminijski silikati osušeni pri srednjim temperaturama, npr. pri 80 do 200°C, sve do uklanjanja adhezijske vode. However, aluminum silicates do not need to be dried at all after production for production according to the invention; even more - and this is of particular advantage - aluminum silicate can be used while it is still wet from production. Aluminum silicates dried at medium temperatures, for example at 80 to 200°C, can also be used for the production of suspension, until the adhesive water is removed.
Veličina čestica pojedinih čestica aluminijskih silikata može biti različita i može biti npr. u rasponu od 0,1 μm do 0,1 mm. Od posebne prednosti je upotreba auminijskih silikata, koji se sastoje od najmanje 80% tež. čestica veličine od 10 do 0,01 μm. Od prednosti je da ovi aluminijski silikati ne sadrže primarne niti sekundarne čestice promjera većeg od 45 μm. Pod sekundarnim česticama podrazumijevaju se veće čestice, stvorene agregacijom primarnih čestica. The particle size of individual aluminum silicate particles can be different and can be, for example, in the range from 0.1 μm to 0.1 mm. Of particular advantage is the use of aluminum silicates, which consist of at least 80% by weight. particle size from 10 to 0.01 μm. It is advantageous that these aluminum silicates do not contain primary or secondary particles with a diameter greater than 45 μm. Secondary particles mean larger particles, created by the aggregation of primary particles.
Glede aglomeracije primarnih čestica u veće tvorevine, posebno dobrom se pokazala primjena aluminijskih silikata još vlažnih od proizvodnje u cilju proizvodnje suspenzije prema pronalasku, jer se je pokazalo da se kod primjene ovih, još vlažnih proizvoda stvaranje aglomeracije praktično potpuno sprečava. Regarding the agglomeration of primary particles into larger formations, the use of aluminum silicates that are still wet from production in order to produce the suspension according to the invention has proven to be particularly good, because it has been shown that when using these, still wet products, the formation of agglomeration is practically completely prevented.
U jednom, posebno pogodnom, obliku izvedbe izuma kao A pomoponenta može se koristi praškasti zeolit tipa A s posebno definiranim spektrom čestica. In one particularly suitable form of embodiment of the invention, powdered zeolite type A with a specially defined spectrum of particles can be used as A auxiliary component.
Takovi praškasti zeoliti mogu se proizvoditi prema DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485. Oni tada imaju date krivulje razdiobe čestica. Such powdered zeolites can be produced according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE -OS 26 51 445, DE-OS 26 51 485. They then have given particle distribution curves.
U jednom posebno pogodnom obliku izvedbe može se primijeniti zeolit tipa A, koji ima razdiobu veličine čestica u skladu s onom opisanom u DE-OS 26 51 485. In one particularly suitable embodiment, zeolite type A can be used, which has a particle size distribution in accordance with that described in DE-OS 26 51 485.
Koncentracija koraponente A treba iznositi prije svega 44 do 55 mas %., posebno 46 do 52 mas. % i više. The concentration of component A should be above all 44 to 55 wt %, especially 46 to 52 wt. % and more.
Komponenta B može se, prije svega, sastojati od smjese dvaju oksoalkohol-etoksilata, pri čemu jedna komponenta treba sadržavati jedan oksoalkohol-etoksilat s 3 do 5,25 mola etilenoksida i imati točku zamućivanja pri 56 - 68,5°C, ponajprije sa 4 - 5 mola EO i točkom zamućenja pri 60 - 67°C, pri čemu ugljikov prsten R ima 10 - 15, ponajprije 12 - 13 C-atoma, a druga (B) komponenta treba biti jedan oksoalkohol-etoksilat s 5,5 do 7,0 mola etilenoksida i s točkom zamućenja pri 70,5 do 80°C, ponajprije 5,75 - 6,5 mola EO i točkom zamućenja pri 71 -77°C, pri čemu ugljikov prsten R ima 10 - 15, ponajprije 12 - 13 C-atoma. Component B can, first of all, consist of a mixture of two oxoalcohol-ethoxylates, whereby one component should contain one oxoalcohol-ethoxylate with 3 to 5.25 moles of ethylene oxide and have a cloud point at 56 - 68.5°C, preferably with 4 - 5 moles of EO and a cloud point at 60 - 67°C, whereby the carbon ring R has 10 - 15, preferably 12 - 13 C-atoms, and the second (B) component should be an oxoalcohol-ethoxylate with 5.5 to 7 ,0 moles of ethylene oxide and with a cloud point at 70.5 to 80°C, preferably 5.75 - 6.5 moles of EO and a cloud point at 71 -77°C, whereby the carbon ring R has 10 - 15, preferably 12 - 13 C-atom.
Oksalkohol-etoksilati mogu se međusobno miješati u omjeru od 9:1 do 1:9, ponajprije id 2:3 do 3:2, posebno od 0,9 do 1,1 do 1,1:0,9. Oxalcohol-ethoxylates can be mixed in a ratio of 9:1 to 1:9, preferably 2:3 to 3:2, especially 0.9 to 1.1 to 1.1:0.9.
Koncentracija komponenata B i C u vodenoj otopini može biti ponajprije od 1 do 2 mas. %, posebno 1,4 do 1,6 mas. %. Ova koncetracija dovoljna je za stabilizaciju suspenzije sadržaja čvrste tvari od 50 mas. % i više. The concentration of components B and C in the aqueous solution can preferably be from 1 to 2 wt. %, especially 1.4 to 1.6 wt. %. This concentration is sufficient to stabilize the suspension with a solid content of 50 wt. % and more.
Komponenta C (svedena na količinu stabilizatora koji se sastoji od komponenata B i C) može se mijenjati s udjelom od 3 do 20 mas. %, ponajprije od 5 do 15 mas. %. U jednom posebno pogodnom obliku izvedbe srednja molekulska masa polietilenglikola može biti 200 do 1000. Component C (reduced to the amount of stabilizer consisting of components B and C) can be changed with a proportion of 3 to 20 wt. %, preferably from 5 to 15 wt. %. In one particularly suitable embodiment, the average molecular weight of polyethylene glycol can be 200 to 1000.
Suspenzija prema izumu ima i tu prednost, da je ispod 25°C stabilna glede taloženja i ima konzistenciju pogodnu za pumpanje. The suspension according to the invention also has the advantage that below 25°C it is stable in terms of precipitation and has a consistency suitable for pumping.
Dalja prednost je to, da je oksoalkohol-etoksilat tekuć pri sobnoj temperaturi i stoga se mora zagrijavati. A further advantage is that the oxoalcohol ethoxylate is liquid at room temperature and therefore must be heated.
Posebna prednost je u tome, da se kod suspenzije prema izumu mogu primijeniti znatno viši postoci čvrste tvari od 50 mas. %. A special advantage is that with the suspension according to the invention, significantly higher percentages of solids of 50 wt. %.
Posve osobita prednost je primjena polietilenglikola u smjesi stabilizatora. Postojanost zeolitne suspenzije pri dodatku polietilenglikola do 15% ostaje bez utjecaja, a tek iznad 20% dodatka polietilenglikola opada stabilizirajući utjecaj smjese tenzida. Suprotno tome, neočekivani pozitivni utjecaji na viskoznost, a posebno na svojstva istjecanja postižu se dodatkom polietilenglikola. U rasponu od 5 - 15% dodatka polietilenglikola dobiva se optimalan sadržaj, koji vodi računa o postojanosti, viskoznosti i svojstvima istjecanja. A very special advantage is the use of polyethylene glycol in the stabilizer mixture. The stability of the zeolite suspension with the addition of polyethylene glycol up to 15% remains unaffected, and only above 20% of the addition of polyethylene glycol does it decrease, stabilizing the influence of the surfactant mixture. On the contrary, unexpected positive effects on the viscosity, and especially on the flow properties, are achieved by the addition of polyethylene glycol. In the range of 5 - 15% addition of polyethylene glycol, the optimal content is obtained, which takes into account stability, viscosity and flow properties.
Načelno, vodene suspenzije, osim navedenih sastojaka A i B i potrebnih polaznih tvari za proizvodnju ovih sastojaka, mogu se držati u relativno malim količinama. Ako se predviđa dalja prerada suspenzije u sredstva za pranje i čišćenje, onda se kod dodatno potrebnih tvari radi naravno i svrhovito o tvarima pogodnim za sastojke sredstava za pranje i čišćenje. In principle, water suspensions, except for the listed ingredients A and B and the necessary starting materials for the production of these ingredients, can be kept in relatively small quantities. If further processing of the suspension into washing and cleaning agents is envisaged, then the additionally required substances are naturally and purposefully substances suitable for the ingredients of washing and cleaning agents.
Suspenzije se mogu proizvoditi jednostavnim miješanjem njihovih sastojaka, pri čemu se aluminijski silikati mogu npr. koristiti kao takovi - ili izravno iz proizvodnje - već vlažni ili u vodenoj suspenziji. Od posebne prednosti je umiješati komponentu B u aluminijske silikate još vlažne od proizvodnje, npr. kao talog odvojen filtriranjem. Suspensions can be produced by simply mixing their ingredients, whereby aluminum silicates can, for example, be used as such - or directly from production - already wet or in aqueous suspension. It is particularly advantageous to mix component B into aluminum silicates still wet from production, for example as a precipitate separated by filtration.
Svakako, mogu se rabiti i već osušeni, tj. aluminijski silikati oslobođeni adhezijske vlage, koji mogu sadržavati vezanu vodu. Of course, they can also be used already dried, i.e. aluminum silicates freed from adhesive moisture, which may contain bound water.
Suspenzija prema izumu odlikuje se visokom postojanošću i drugim prednostima. The suspension according to the invention is characterized by high stability and other advantages.
Njeno stabilizirajuće djelovanje posebno je vrijedno kod aluminijskih silikata veličine čestica od 1 do 30 μm. Oni se mogu pumpati tako da omogućuju jednostavno rukovanje vlažnih aluminijskih silikata. Čak i nakon duljih prekida pumpanja ove suspenzije mogu se bez teškoća ponovno pumpati. Na osnovu njihove visoke postojanosti suspenzije se mogu transportirati u uobičajenim vagonima cisternama, bez straha od oblikovanja neupotrebljivih odnosno štetnih ostataka. Time su ove suspenzije odlične kao isporučni oblik aluminijskih silikata za isporuku npr. proizvođačima sredstava za pranje. Its stabilizing effect is especially valuable for aluminum silicates with particle sizes from 1 to 30 μm. They can be pumped to allow easy handling of wet aluminum silicates. Even after longer pumping interruptions, these suspensions can be pumped again without difficulty. Due to their high stability, suspensions can be transported in ordinary tank wagons, without fear of the formation of unusable or harmful residues. Thus, these suspensions are excellent as a delivery form of aluminum silicates for delivery, for example, to manufacturers of detergents.
Ove suspenzije prema izumu posebno su pogodne za daljnju preradu u naizgled suhe, sipke proizvode, pogodne za prskanje, dakle za proizvodnju praškastih aluminijskih silikata. These suspensions according to the invention are particularly suitable for further processing into apparently dry, loose products, suitable for spraying, i.e. for the production of powdered aluminum silicates.
Prilikom dovođenja vodene suspenzije do uređaja za sušenje ne nastaju bilo kakovi smetajući ostaci. Dalje se je pokazalo, da suspenzija prema izumu omogućuje preradu do proizvoda s izuzetno malo prašine. When feeding the aqueous suspension to the drying device, no annoying residues are formed. Furthermore, it was shown that the suspension according to the invention enables processing to a product with extremely little dust.
Temeljem njihove posebne postojanosti suspenzije prema izumu mogu se rabiti već kao takove, tj. bez dalje prerade, sa ili bez dodataka za pranje, bijeljenje i/ili čišćenje, npr. kao sredstva za omekšavanje vode, sredstava za pranje i čišćenje i posebno kao blaga tekuća sredstva za ribanje povećane postojanosti suspenzije. Due to their special stability, the suspensions according to the invention can be used as such, i.e. without further processing, with or without additives for washing, bleaching and/or cleaning, e.g. as water softeners, washing and cleaning agents and especially as mild liquid scouring agents increased suspension stability.
Posebno važna primjena suspenzije je u daljnjoj preradi u naizgled suha, rastresita i sredstva za pranje i čišćenje pogodna za prskanje, koja pored sastojaka u suspenziji sadrže i druge spojeve. A particularly important application of the suspension is in the further processing into apparently dry, loose washing and cleaning agents suitable for spraying, which, in addition to the ingredients in the suspension, also contain other compounds.
Suspenzije prema izumu posebno su pogodne za proizvodnju praškastih sredstava za pranje i čišćenje. The suspensions according to the invention are particularly suitable for the production of powder detergents and cleaning agents.
Kod proizvodnje ovakovih sredstava polazi se od vodene, tekuće otopine prethodne smjese pojedinih sastojaka i prevodi ju se na uobičajen način u rastresiti proizvod. Pri tome se gore definirani aluminijski silikat rabi u obliku suspenzije prema izumu. Suspenzije prema izumu mogu se prerađivati proizvoljnim poznatim postupcima u čvrsta, rastresita sredstva za pranje i čišćenje. In the production of such products, the starting point is an aqueous, liquid solution of the previous mixture of individual ingredients and it is translated in the usual way into a loose product. The aluminum silicate defined above is used in the form of a suspension according to the invention. The suspensions according to the invention can be processed by arbitrary known procedures into solid, loose washing and cleaning agents.
Pri proizvodnji praškastih sredstava za pranje i čišćenje posebno se postupa tako, da se suspenzija prema izumu - npr. iz nekog spremnika - pomiješa s barem jednim sastojkom za pranje i čišćenje ili bijeljenje, a zatim se ta smjesa prevodi proizvoljnim postupkom u praškasti proizvod. Pogodno je da se dodaje sredstvo za stvaranje kompleksa, tj. jedan spoj sposoban za kompleksno vezanje i ona odgovornih za tvrdoću vode, posebno zemno alkalnih metala, kao magnezija i kalcija. In the production of powder detergents, the special procedure is to mix the suspension according to the invention - for example from a container - with at least one ingredient for washing and cleaning or bleaching, and then this mixture is converted into a powder product by an arbitrary process. It is convenient to add a complexing agent, i.e. a compound capable of complex binding and those responsible for the hardness of water, especially alkaline earth metals, such as magnesium and calcium.
U općem slučaju pri proizvodnji sredstava za pranje i čišćenje suspenzija prema izumu spaja se ponajprije s barem jednim tenzidom topivim u vodi, koji ne pripada mogućim sastojcima komponente B. In the general case, during the production of detergents and cleaning agents, the suspension according to the invention is first combined with at least one water-soluble surfactant, which does not belong to the possible components of component B.
U proizvodnji sredstava za pranje i čišćenje postoje različite inačice. In the production of washing and cleaning products, there are different versions.
Npr., sa suspenzijom prema izumu mogu se sjediniti tvari sposobne za vezanje kristalne vode, na svrhovit način prskanjem suspenzije na spojeve sposobne za vezanje kristalne vode, prethodno stavljene u mješalicu, tako da se stalnim miješanjem na kraju dobije čvrst, naizgled suhi proizvod. For example, substances capable of binding crystal water can be combined with the suspension according to the invention, in a purposeful way by spraying the suspension on the compounds capable of binding crystal water, previously placed in the mixer, so that a solid, apparently dry product is obtained at the end with constant mixing.
Međutim, bolje je suspenzije prema izumu pomiješati kao rijetko blago ("slurry") s najmanje još jednim spojem koji djeluje u smislu pranja ili čišćenja i podvrgnuti postupku sušenja raspršivanjem. Pri tome pokazuju se nadalje iznenađujuće prednosti suspenzije ovih aluminijskih silikata. Naime, pokazalo se da se upotrebom suspenzije prema izumu u postupku sušenja raspršivanjem dobivaju proizvodi s vrlo malo prašine. Proizvodi dobiveni postupkom sušenja raspršivanjem pokazuju veliku sposobnost vezanja kalcija i dobro se umrežavaju. However, it is better to mix the suspensions according to the invention as a slurry with at least one other washing or cleaning compound and subject them to a spray drying process. In addition, the surprising advantages of the suspension of these aluminum silicates are shown. Namely, it has been shown that using the suspension according to the invention in the spray drying process produces products with very little dust. The products obtained by the spray drying process show a high ability to bind calcium and crosslink well.
Sredstva za pranje proizvedena upotrebom suspenzije prema izumu mogu se sastavljati na najrazličitije načine. U općem slučaju njima se dodaje barem jedno sredstvo za dispergiranje koje ne pripada izumu od dotičnih aluminijskih silikata, i to tenzid topiv u vodi. Također se stavlja barem još jedan spoj koji djeluje u smislu pranja, čišćenja ili izbjeljivanja i anorganske ili organske naravi, kao što je gore definirani aluminijski silikat, koji djeluje kao spoj koji veže kalcij. Osim toga među takovim sredstvima mogu biti i druge uobičajene tvari, obično u malim količinama. Detergents produced using the suspension according to the invention can be assembled in a variety of ways. In the general case, at least one dispersing agent that does not belong to the invention of the respective aluminum silicates, namely a water-soluble surfactant, is added to them. At least one other compound which acts in terms of washing, cleaning or bleaching and of an inorganic or organic nature, such as the aluminum silicate defined above, which acts as a calcium binding compound is also added. In addition, such agents may include other common substances, usually in small amounts.
Primjeri Examples
Talog zeolita A sa stabilizatorom, odvojen filtriranjem, miješa se po potrebi uz dodatak vode. The precipitate of zeolite A with stabilizer, separated by filtration, is mixed if necessary with the addition of water.
Kao stabilizatori dodaju se komponente B i C. Navodi se i stupanj etoksiliranja EO. Upotrijebljen talog zeolita A odvojen filtriranjem proizvodi se prema DE-OS 26 51 485 i ima tamo naveden spektar čestica. Components B and C are added as stabilizers. The degree of ethoxylation of the EO is also indicated. The zeolite A precipitate used, separated by filtration, is produced according to DE-OS 26 51 485 and has the particle spectrum specified there.
Za provedbu primjera 50 kg nestabilizirane suspenzije zeolita miješa se jedan sat pri 500 o/min uz dodatak vode prema potrebi u mješalici Ekato-Standardmix. To implement the example, 50 kg of unstabilized zeolite suspension is mixed for one hour at 500 rpm with the addition of water as needed in an Ekato-Standardmix mixer.
Nakon dodatka 1,5 mas. % stabilizatorske smjese miješa se još 10 minuta pri istoj brzini. After adding 1.5 wt. % of the stabilizer mixture is mixed for another 10 minutes at the same speed.
Točke zamućenja upotrijebljenih stabilizatora navedene su u tablici I. The cloud points of the stabilizers used are listed in Table I.
Tablica I. Table I.
Točke zamućenja prema DIN-u 53 917 primijenjenih oksoalkohol-etoksilata (5 g tenzida na 25 g 25%-tne otopine butildialikola). Cloud points according to DIN 53 917 of the applied oxoalcohol ethoxylates (5 g of surfactants on 25 g of a 25% butyldialycol solution).
[image] [image]
Tenzidi iz proizvodnog procesa sadrže polietilenglikol (PEG) u količinama od 1%. Radi provjere utjecaja PEG-a na postojanost i svojstva tecivosti smjesi od 1:1 obaju pojedinačnih tenzida dodaje se PEG, srednje molekulske mase od otprilike 800, u takovim količinama 1:1 da ukupni sadržaj PEG-a bude oko 7%, odnosno 15% i 20 mas. %. Provjera postojanosti vrši se nakon 3 dana (tablica 2), dok se provjera viskoznosti i istjecanja vrši istog dana (tablice 3 i 4). Surfactants from the production process contain polyethylene glycol (PEG) in amounts of 1%. In order to check the influence of PEG on the stability and fluidity properties, PEG, with an average molecular weight of approximately 800, is added to a 1:1 mixture of both individual surfactants in such 1:1 amounts that the total PEG content is about 7% and 15% and 20 wt. %. Stability is checked after 3 days (table 2), while viscosity and flow are checked on the same day (tables 3 and 4).
Tablica II Table II
Stabilizacija suspenzije zeolita pomoću oksoalkoholetoksilata sa C12/13-dužinom lanca (sadržaj čvrste tvari u suspenziji zeolita: 49%). Stabilization of zeolite suspension using oxoalcohol ethoxylates with C12/13-chain length (solid content in zeolite suspension: 49%).
[image] [image]
Ocjenjivanje homogenosti i istjecanja vršeno je prema školskom sistemu (1 = vrlo dobro, do 5 = slabo). Homogeneity and flow were evaluated according to the school system (1 = very good, up to 5 = poor).
Tablica III Table III
Mjerenje viskoznosti na stabiliziranim suspenzijama zeolita pri različitim temperaturama (mjerni uređaj Brookfield RTV, osovina 4). Viscosity measurement on stabilized zeolite suspensions at different temperatures (Measuring device Brookfield RTV, axis 4).
[image] [image]
Tablica IV Table IV
Određivanje vremena istjecanja pomoću vrča br. 4 prema Determining the expiration time using pitcher no. 4 according to
DIN-u (DIN 53 211) pri 22°C. to DIN (DIN 53 211) at 22°C.
[image] [image]
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4109501A DE4109501A1 (en) | 1991-03-22 | 1991-03-22 | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
YU28492A YU48184B (en) | 1991-03-22 | 1992-03-20 | WATER STABLE SUSPENSION OF WATER SOLUBLE SILICATES, CAPABLE OF BINDING CALCIUM IONS AND THEIR APPLICATION IN THE PRODUCTION OF WASHING AND CLEANING PRODUCTS |
Publications (2)
Publication Number | Publication Date |
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HRP920669A2 true HRP920669A2 (en) | 1997-06-30 |
HRP920669B1 HRP920669B1 (en) | 2000-08-31 |
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HR920669A HRP920669B1 (en) | 1991-03-22 | 1992-09-30 | Aqueous, stable suspensions of water insoluble silicates which are able to bind calcium ions and their use in the production of washing and cleaning agents |
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US (1) | US5298185A (en) |
EP (1) | EP0504564B1 (en) |
JP (1) | JPH0747758B2 (en) |
KR (1) | KR950005381B1 (en) |
AT (1) | ATE109504T1 (en) |
CA (1) | CA2063662C (en) |
CZ (1) | CZ282217B6 (en) |
DE (2) | DE4109501A1 (en) |
DK (1) | DK0504564T3 (en) |
EE (1) | EE02963B1 (en) |
ES (1) | ES2057929T3 (en) |
FI (1) | FI921213A (en) |
HR (1) | HRP920669B1 (en) |
HU (1) | HU211435B (en) |
LV (1) | LV10970B (en) |
PL (1) | PL169585B1 (en) |
RU (1) | RU2061742C1 (en) |
SI (1) | SI9210284B (en) |
SK (1) | SK278100B6 (en) |
TR (1) | TR26395A (en) |
UA (1) | UA25955C2 (en) |
YU (1) | YU48184B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4203789A1 (en) * | 1992-02-10 | 1993-08-12 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
DE4303320C2 (en) * | 1993-02-05 | 1995-12-21 | Degussa | Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor |
GB9520024D0 (en) * | 1995-09-30 | 1995-12-06 | Procter & Gamble | Detergent composition |
Family Cites Families (10)
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GB8308508D0 (en) * | 1983-03-28 | 1983-05-05 | Ici Plc | Detergent compositions |
FR2568790B1 (en) * | 1984-08-10 | 1990-01-12 | Rhone Poulenc Chim Base | PROCESS FOR OBTAINING A STABLE AND PUMPABLE AQUEOUS SUSPENSION OF ZEOLITE AND SUSPENSION THUS OBTAINED |
DE3444311A1 (en) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
US4846992A (en) * | 1987-06-17 | 1989-07-11 | Colgate-Palmolive Company | Built thickened stable non-aqueous cleaning composition and method of use, and package therefor |
DE3735618A1 (en) * | 1987-01-30 | 1988-08-11 | Degussa | DETERGENT PICTURES |
DE3715051A1 (en) * | 1987-05-06 | 1988-11-17 | Degussa | PHOSPHATE-FREE DETERGENT BUILDER |
EP0294694B1 (en) * | 1987-06-06 | 1993-11-10 | Degussa Aktiengesellschaft | Aquoeus stable suspensions of water insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning compositions |
DE3818657A1 (en) * | 1987-06-06 | 1988-12-15 | Degussa | Stable aqueous suspension of silicates which are insoluble in water and capable of binding calcium ions, and the use thereof for producing detergents and cleaners |
JP2796535B2 (en) * | 1990-06-01 | 1998-09-10 | ライオン株式会社 | Zeolite-containing liquid detergent composition |
US5205757A (en) * | 1991-04-01 | 1993-04-27 | Chris Hertelendy | Electrical connector |
-
1991
- 1991-03-22 DE DE4109501A patent/DE4109501A1/en not_active Ceased
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1992
- 1992-02-04 AT AT92101761T patent/ATE109504T1/en not_active IP Right Cessation
- 1992-02-04 EP EP92101761A patent/EP0504564B1/en not_active Expired - Lifetime
- 1992-02-04 DE DE59200336T patent/DE59200336D1/en not_active Expired - Fee Related
- 1992-02-04 ES ES92101761T patent/ES2057929T3/en not_active Expired - Lifetime
- 1992-02-04 DK DK92101761.2T patent/DK0504564T3/en active
- 1992-03-17 US US07/853,179 patent/US5298185A/en not_active Expired - Fee Related
- 1992-03-17 TR TR92/0259A patent/TR26395A/en unknown
- 1992-03-19 JP JP4063497A patent/JPH0747758B2/en not_active Expired - Fee Related
- 1992-03-20 SK SK847-92A patent/SK278100B6/en unknown
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- 1992-03-20 HU HU9200935A patent/HU211435B/en not_active IP Right Cessation
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- 1992-03-20 KR KR1019920004584A patent/KR950005381B1/en not_active IP Right Cessation
- 1992-03-20 CZ CS92847A patent/CZ282217B6/en not_active IP Right Cessation
- 1992-03-20 RU SU925011125A patent/RU2061742C1/en active
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Also Published As
Publication number | Publication date |
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JPH0747758B2 (en) | 1995-05-24 |
FI921213A0 (en) | 1992-03-20 |
LV10970B (en) | 1996-06-20 |
TR26395A (en) | 1995-03-15 |
HUT60520A (en) | 1992-09-28 |
JPH0578695A (en) | 1993-03-30 |
EE02963B1 (en) | 1997-02-17 |
YU28492A (en) | 1994-06-10 |
FI921213A (en) | 1992-09-23 |
SK278100B6 (en) | 1996-01-10 |
CS84792A3 (en) | 1992-10-14 |
YU48184B (en) | 1997-07-31 |
US5298185A (en) | 1994-03-29 |
CA2063662A1 (en) | 1992-09-23 |
LV10970A (en) | 1995-12-20 |
ATE109504T1 (en) | 1994-08-15 |
CZ282217B6 (en) | 1997-06-11 |
KR920018206A (en) | 1992-10-21 |
EP0504564B1 (en) | 1994-08-03 |
PL293926A1 (en) | 1992-11-30 |
SI9210284B (en) | 1998-06-30 |
CA2063662C (en) | 1996-01-09 |
EP0504564A1 (en) | 1992-09-23 |
HRP920669B1 (en) | 2000-08-31 |
DE4109501A1 (en) | 1992-09-24 |
ES2057929T3 (en) | 1994-10-16 |
HU211435B (en) | 1995-11-28 |
DK0504564T3 (en) | 1994-11-14 |
RU2061742C1 (en) | 1996-06-10 |
PL169585B1 (en) | 1996-08-30 |
DE59200336D1 (en) | 1994-09-08 |
HU9200935D0 (en) | 1992-06-29 |
UA25955C2 (en) | 1999-02-26 |
SI9210284A (en) | 1995-06-30 |
KR950005381B1 (en) | 1995-05-23 |
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